WO2008125214A1 - 4-(4-trifluoromethyl-3-thiobenzoyl)pyrazoles, and use thereof as herbicides - Google Patents

Abstract

Disclosed are 4-(4-trifluoromethyl-3-thiobenzoyl)pyrazoles of general formula (I) as well as the use thereof as herbicides. In said formula (I), R1, R2, R3, and R4 represent radicals such as hydrogen and organic radicals such as alkyl, and Y represents hydrogen or a protective group such as tosyl.

Description

 description

4- (4-trifluoromethyl-3-thiobenzoyl) pyrazoles and their use as herbicides

The invention relates to the technical field of herbicides, in particular that of herbicides for the selective control of weeds and grass weeds in crops.

It is already known from various publications that certain benzoylpyrazoles possess herbicidal properties. Thus, DE 2513750, EP 0 352 543, EP 0 203 428, WO 97/41106, WO 00/03993 and US 4,557,753 mention benzoylpyrazoles which are substituted by various radicals.

However, the compounds known from these publications often show inadequate herbicidal activity. The object of the present invention is therefore to provide herbicidally active compounds with improved herbicidal properties compared with the compounds known from the prior art.

It has now been found that certain 4-benzoylpyrazoles whose phenyl ring carries a thio group in the 3-position and a trifluoromethyl group in the 4-position are particularly suitable as herbicides. An object of the present invention are 4- (4-trifluoromethyl-3-thiobenzoyl) pyrazoles of the formula (I) or salts thereof

(I).

wherein

R ¹ is (C _r C ₄ ) -alkyl,

R ² is hydrogen or (C 1 -C ₄ ) -alkyl,

R ³ is (C 1 -C 4) alkyl,

R ⁴ is (C _r C ₄ ) -alkyl,

Y is hydrogen, (C ₁ -C ₆ ) -alkylsulfonyl, (C ₁ -O-C ₁ -C ₆ -alkylsulfonyl, or in each case by m identical or different radicals from the group consisting of halogen, (C ₁ -C ₄ ) -Alkyl and (C 1 -C ₄ ) -alkoxy-substituted phenylsulfonyl, thiophenyl-2-sulfonyl, benzoyl, benzoyl- (C 1 -C ₆ ) -alkyl or benzyl,

m is 0, 1, 2 or 3,

n is 0, 1 or 2.

In the case where Y is hydrogen, the compounds of the formula (I) according to the invention can occur in different tautomeric structures, depending on external conditions, such as solvent and pH:

Depending on the nature of the substituents, the compounds of the general formula (I) contain an acidic proton which can be removed by reaction with a base. Suitable bases are, for example, hydrides, hydroxides and carbonates of lithium, sodium, potassium, magnesium and calcium and ammonia and organic amines such as triethylamine and pyridine. Likewise, salts can be formed by addition of organic acids, such as formic or acetic acid, and inorganic acids, such as phosphoric, hydrochloric or sulfuric acid. Such salts are also the subject of the invention.

In formula (I) and all subsequent formulas, alkyl radicals having more than two carbon atoms may be straight-chain or branched. Alkyl radicals mean e.g. Methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1, 3-dimethylbutyl. Halogen is fluorine, chlorine, bromine or iodine. Tosyl means 4-methylphenylsulfonyl.

If a group is repeatedly substituted by radicals, it is to be understood that this group is substituted by one or more identical or different radicals. Depending on the nature and linkage of the substituents, the compounds of the general formula (I) can exist as stereoisomers. For example, if one or more asymmetric carbon atoms or sulfur atoms are present (ie in the case of sulfoxides), enantiomers and diastereomers may occur.

Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods. Similarly, stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants. The invention also relates to all stereoisomers and mixtures thereof which include but are not specifically defined by the general formula (I).

Preference is given to compounds of the general formula (I) in which

R ¹ is methyl or ethyl,

R ² is hydrogen, methyl or ethyl,

R ³ is methyl or ethyl,

R ⁴ is methyl or ethyl,

Y is hydrogen, (C ₁ -C ₃ ) -alkylsulfonyl, (C ₁ -C ₂ ) -alkoxy- (C ₁ -C ₄ ) -alkylsulfonyl, or phenylsulfonyl which is each substituted by m-methyl groups, thiophenyl-2-sulfonyl, benzoyl, benzoyl- (C 1 -C ₆ ) -alkyl or benzyl,

m is 0 or 1,

n is 0, 1 or 2.

Particular preference is given to compounds of the general formula (I) in which R ¹ is methyl or ethyl,

R ₃ 2 is hydrogen, methyl or ethyl,

means methyl or ethyl,

R ⁴ is methyl or ethyl,

Y is hydrogen,

n is 0, 1 or 2.

In all of the formulas below, the substituents and symbols, unless otherwise defined, have the same meaning as described for formula (I).

Compounds according to the invention in which Y is hydrogen can be synthesized, for example, according to the procedure given in Scheme 1 and from Acta Chem. Scand. 13, (1959), 1668-1670 known methods by base-catalyzed reaction of a Benzoesäurehalogenids (III) with a pyrazolone (II) or according to the method shown in Scheme 2 and, for example, from EP-A 0,186,117 known methods by base-catalyzed reaction of a Benzoesäurehalogenids (III ) are prepared with a pyrazolone (II) and subsequent rearrangement.

(II) (HI) (I *) Scheme 2

acetone

(I *)

According to Scheme 3, compounds according to the invention in which Y has a meaning other than hydrogen are expediently obtained from the compounds obtainable according to Scheme 1 or 2 by base-catalyzed reaction with a suitable acylating agent YX of the formula (V) in which X is a leaving group such as halogen, produced. Such methods are known to those skilled in principle and described for example in DOS 25 13 750.

Scheme 3

(Ia *) (V) (I) Compounds of the invention may also be prepared according to the method disclosed in Scheme 4 and known from WO 98/42678 by reaction of a pyrazolone (II) with a halo-benzoic acid (IIIa), followed by nucleophilic aromatic substitution by a thio compound HS-R ³ and optionally oxidation of the thio group getting produced. In this L means, for example, chlorine, bromine, iodine or trifluoromethylsulfonyl. Such substitution reactions are known in the art and described for example in Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. E 11, extension and follow-up volumes to the fourth edition 1985, p 174 et seq.

Scheme 4

acetone

The abovementioned compounds of the formula (III) can be prepared, for example, by reaction with acid chlorides from the compounds of the formula (IIIb) according to methods known to the person skilled in the art.

(IIIb)

Compounds of the formula (III) and (UIb) in which R ³ , R ⁴ and n are as defined for formula (I) are novel and likewise the subject of the present application.

The starting compounds used in the above schemes are either commercially available or can be prepared by methods known per se. For example, the pyrazolones of the formula (II) can be prepared according to the methods described in EP-A 0 240 001 and J. Prakt. Chem. 315, 382, (1973) and the benzoyl chlorides of the formula (III) are prepared by the processes described in EP-A 0 527 036 and WO 03/014071.

The compounds of the formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Even difficult to control perennial weeds, which expel from rhizomes, rhizomes or other permanent organs, are well detected by the active ingredients. It is usually irrelevant whether the substances are applied in the pre-sowing, pre-emergence or postemergence process. Specifically, by way of example, some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain species. On the side of the monocotyledonous weed species, for example, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus species from the annuelle group and on the side of perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperusarten are well detected. In dicotyledonous weed species, the spectrum of activity extends to species such as Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Sida, Matricaria and Abutilon on the annall side and Convolvulus, Cirsium, Rumex and Artemisia to perennial weeds. Harmful plants occurring under the specific culture conditions in rice such as Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also excellently controlled by the active compounds according to the invention. If the compounds according to the invention are applied to the surface of the earth before germination, then either the emergence of the weed seedlings is completely prevented, or the weeds are completely prevented grow to the cotyledon stage but then stop growing and eventually die off after three to four weeks. When the active ingredients are applied to the green parts of plants post-emergence, a drastic growth stop also occurs very rapidly after the treatment and the weed plants remain in the existing at the time of application

Growth stage or die completely after a certain time, so that in this way harmful to the crops weed competition is eliminated very early and sustainably. In particular, the compounds according to the invention show an outstanding activity against Apera spica venti, Chenopodium album, Lamium purpureum, Polygonum convulvulus, Stellaria media, Veronica hederifolia, Veronica persica and Viola tricolor.

Although the compounds of the present invention have excellent herbicidal activity against mono- and dicotyledonous weeds, crops of economically important crops such as e.g. Wheat, barley, rye, rice, maize, sugar beet, cotton and soya only marginally or not at all damaged. In particular, they have excellent compatibility in cereals, such as wheat, barley and maize, especially wheat. For these reasons, the present compounds are very well suited for the selective control of undesired plant growth in agricultural crops or in ornamental plantings.

Due to their herbicidal properties, the active compounds can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants. The transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties concern, for example, the crop in terms of quantity, quality, shelf life, composition and special ingredients. So are transgenic Plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop.

Preference is given to the use of the compounds of the formula (I) according to the invention or their salts in economically important transgenic crops of useful and ornamental plants, e.g. of cereals such as wheat, barley, rye, oats, millet, rice, manioc and maize or also crops of sugar beet, cotton, soya, rapeseed, potato, tomato, pea and other vegetables. Preferably, the compounds of the formula (I) can be used as herbicides in crop plants which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.

Conventional ways of producing new plants which have modified properties in comparison to previously occurring plants consist, for example, in classical breeding methods and the production of mutants. Alternatively, new plants with altered properties can be generated by genetic engineering techniques (see, e.g., EP-A-0221044, EP-A-0131624). For example, genetic modifications of crops have been described in several cases to modify the starch synthesized in the plants (e.g., WO 92/11376, WO 92/14827,

WO 91/19806), transgenic crop plants which are active against certain glufosinate-type herbicides (cf., for example, EP-A-0242236, EP-A-242246) or glyphosate (WO 92/00377) or the sulfonylureas (EP-A-0257993, US-A-5013659) are transgenic crops, for example cotton, capable of producing Bacillus thuringiensis toxins (Bt toxins) which render the plants resistant to certain pests (EP-A-0142924, EP-A-0193259 ). transgenic crops with modified fatty acid composition (WO 91/13972). Numerous molecular biology techniques that can be used to produce novel transgenic plants with altered properties are known in principle; See, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd Ed. CoId Spring Harbor Laboratory Press, ColD Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431).

For such genetic engineering, nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence alteration by recombination of DNA sequences. By means of the above-mentioned standard methods, e.g. Base exchanges are made, partial sequences removed or natural or synthetic sequences added. For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments.

The production of plant cells having a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a cosuppression effect or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product.

For this purpose, DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical.

In the expression of nucleic acid molecules in plants, the synthesized protein may be located in any compartment of the plant cell. Around but to achieve localization in a particular compartment, for example, the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).

The transgenic plant cells can be regenerated to whole plants by known techniques. The transgenic plants may in principle be plants of any plant species, i. both monocotyledonous and dicotyledonous plants. Thus, transgenic plants are available which have altered properties by overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences.

In the application of the active compounds according to the invention in transgenic crops, in addition to the effects observed in other crops on harmful plants, effects which are specific for the application in the respective transgenic crop often occur, for example a modified or specially extended weed spectrum which can be controlled

Expense amounts that can be used for the application, preferably good compatibility with the herbicides to which the transgenic culture is resistant, and influencing the growth and yield of transgenic crops. The invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

In addition, the substances according to the invention have excellent growth-regulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant ingredients and facilitate harvesting, eg by triggering desiccation and stunted growth. Furthermore They are also suitable for the general control and inhibition of unwanted vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous cultures, as storage can be reduced or completely prevented.

The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations. Another object of the invention therefore also herbicidal agents containing compounds of formula (I). The compounds of the formula (I) can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions .

Suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of micro-, spray-, Elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in: Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY , 1973; K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.

The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticides Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry "; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, NY 1963; McCutcheon's "Detergents and Emulsifiers Annual, "MC Publ. Coφ., Ridgewood NJ, Sisley and Wood," Encyclopedia of Surface Active Agents ", Chem. Publ. Co. Inc., NY 1964; Schonfeldt," Grenzaktive Oxyoxidaddukte ", Wiss. Verlagsgesell., Stuttgart 1976 Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Injectable powders are preparations which are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agents, dispersants), eg polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates in addition to the active substance except a diluent or inert substance. 2,2 ^l -dinaphthylmethane-6,6'-disulphonic acid sodium, lignosulphonic acid sodium, dibutylnaphthalenesulphonic acid sodium or oleoylmethyltaurine acid. To prepare the wettable powders, the herbicidal active ingredients are finely ground, for example in customary apparatus such as hammer mills, blower mills and air jet mills, and mixed simultaneously or subsequently with the formulation auxiliaries.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers). Examples of suitable emulsifiers are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as

Fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxethylenesorbitan esters such as polyoxyethylene sorbitan fatty acid esters. Dusts are obtained by grinding the active substance with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding using commercially available bead mills and, if appropriate, addition of surfactants, as described, for example, in US Pat. are already listed above for the other formulation types.

Emulsions, e.g. Oil-in-water emulsions (EW) can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, as described e.g. listed above for the other formulation types.

Granules can either be prepared by atomizing the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired in admixture with fertilizers.

Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.

For the preparation of plate, fluidized bed, extruder and spray granules, see for example methods in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; JE Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff .; "Perry's Chemical Engineer's Handbook," 5th Ed., McGraw-Hill, New York 1973, pp. 8-57. For more details on pesticide formulation see, for example, GC Klingman, "Weed Control as a Science," John Wiley and Sons, Inc., New York, 1961, pp. 81-96, and JD Freyer, SA Evans, "Weed Control Handbook." 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

The agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula (I). In wettable powders, the drug concentration is e.g. about 10 to 90 wt .-%, the balance to 100 wt .-% consists of conventional formulation ingredients. For emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%. Dusty formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the active substance formulations mentioned optionally contain the customary adhesion, wetting, dispersing, emulsifying, penetrating, preserving, antifreeze and solvent, fillers, carriers and dyes, antifoams, evaporation inhibitors and the pH and the Viscosity-influencing agent.

On the basis of these formulations, combinations with other pesticidally active substances, such as e.g. Insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a ready-made formulation or as a tank mix.

As a combination partner for the active compounds according to the invention in

Mixing formulations or in the tank mix, for example, known active ingredients can be used bar, as described for example in Weed Research 26, 441-445 (1986) or "The Pesticide Manual, 11th edition, The British Crop Protection Council and the Royal Soc

Chemistry, 1997 and cited there literature. As known

Herbicides which may be combined with the compounds of formula (I) are e.g. to name the following active ingredients (Note: The compounds are either with the "common name" according to the International Organization for Standardization

(ISO) or with the chemical name, possibly together with a common name

Code number designated): acetochlor; acifluorfen; aclonifen; AKH 7088, i. [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetic acid and acetic acid methyl ester; alachlor; alloxydim; ametryn; amidosulfuron; amitrol; AMS, i. ammonium sulfamate; anilofos; asulam; atrazine; azimsulfurones (DPX-A8947); aziprotryn; barban; BAS 516H, i. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butraline; butylate; cafenstrole (CH-900); carbetamide; cafentrazone; CDAA, i. 2-chloro-N, N-di-2-propenylacetamide; CDEC, i. Diethyldithiocarbamic acid 2-chlorallylester; chlomethoxyfen; chloramben; chlorazifop-butyl; chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlorthiamid; cinmethylin; cinosulfuron; clethodim; clodinafop and its

Ester derivatives (e.g., clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cumyluron (JC 940); cyanazine; cycloate; Cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (e.g., butyl ester, DEH

112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon; desmedipham; Desmetryn; di-allate; dicamba; dichlobenil; dichloroprop; diclofop and its esters such as diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone, clomazone; dimethipin; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 77, i.

5-cyano-1- (1, 1-dimethylethyl) -N-methyl-1H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; Ethidimuron; ethiozin; ethofumesate; F5231, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide; ethoxyfen and its esters (eg

Ethyl ester, HN-252); etobenzanide (HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and their esters, e.g. fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron; fluazifop and fluazifop-P and their esters, e.g. fluazifop-butyl and fluazifop-p-butyl; fluchloralin; flucarbazone; flufenacet; flumetsulam; flumeturon; flumiclorac and its esters (e.g., pentyl ester,

S-23031); flumioxazine (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); fluridone; flurochloridone; fluroxypyr; flurtamone; fomesafen; foramsulfuron; fosamine; furyloxyfen; glufosinate; glyphosate; halo safen; halosulfuron and its esters (e.g., methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P (= R-haloxyfop) and its esters; hexazinone; imazapyr; imazamethabenz-methyl; imazaquin and salts such as the ammonium salt; ioxynil; imazethamethapyr; imazethapyr; imazosulfuron; iodosulfuron-methyl-sodium; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; mesosulfuron; mesotrione; metamitron; metazachlor; metham; methabenzthiazuron; methazole; methoxyphenone; methyldymron; metabenzuron, methobenzuron; metobromuron; metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monolinuron; monuron; monocarbamide dihydrogen sulfates; MT 128, i.

6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.

N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone; phenisopham; phenmedipham; picloram; pinoxaden; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodi amines; profluralin; proglinazine-ethyl; prometon; prometryne; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochlor; propoxycarbazone; Propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyrazolinate; pyrazon; pyrasulfotole; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate; pyrithiobac (KIH-2031); pyroxofop and its esters (eg propargyl esters); quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives eg quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, ie 2- [4-chloro-2-fluoro-5- (2-propynyloxy) -phenyl] -4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; sulcotrione; sulfentrazone (FMC-97285, F-6285); sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); TCA; tebutam (GCP-5544); tebuthiuron; tembotrione; terbacil; terbucarb; terbuchlor; terbumeton; Terbuthylazine; terbutryn; TFH 450, ie N, N-diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1 H-1, 2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiazafluron; thiencarbazone; thiazopyr (Mon-13200); thidiazimin (SN-24085); thiobencarb; thifensulfuron-methyl; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron and esters (eg, methyl ester, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, ie 5-phenoxy-1- [3- (trifluoromethyl) -phenyl] -1H-tetrazole; UBH-509; D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; Dowco-535; DK-8910; V-53482; PP-600; MBH-001; KIH-9201; ET-751; KIH-6127 and KIH-2023.

For use, the formulations present in commercial form are optionally diluted in the usual manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dusty preparations, ground or spreading granules and sprayable

Solutions are usually no longer diluted with other inert substances before use.

With the external conditions such as temperature, humidity, the type of herbicide used, u.a. varies the required application rate of

Compounds of the formula (I). It can fluctuate within wide limits, eg between 0.001 and 1.0 kg / ha or more of active substance, but is preferably between 0.005 and 750 g / ha.

The following examples illustrate the invention.

A. Chemical examples

Preparation of 1-ethyl-4- (3 ^{'-ethylsulfonyl-2'} -methyl-4 ^{'-trifluoromethyl)} benzoyl-5-hydroxypyrazole Step 1: 3-fluoro-2-methyl-4-trifluoromethyl-benzoic acid

25.0 g (120.1 mmol) of 3-fluoro-4-trifluoromethylbenzoic acid were dissolved in 250 ml of THF, and 100.9 ml (2.5M in hexane, 252.3 mmol) n-butyllithium were added at -40 ⁰ C dropwise. The mixture was stirred for 3.5 h, then a solution of 51.2 g (360.4 mmol) of iodomethane in 50 ml of dry THF was added dropwise. The mixture was stirred for 16 h, after which the temperature slowly rose to room temperature (RT) after half an hour. For workup, 150 ml of 1 M HCl were added carefully. The mixture was extracted with diethyl ether, then the organic phase was extracted with 1 M NaOH. The aqueous phase was acidified and then extracted with diethyl ether. The organic phase was washed with water, dried and freed from the solvent. The residue was stirred with n-heptane and the solid was separated via filtration. 13.5 g of the clean product were isolated.

Step 2: 3-Ethylthio-2-methyl-4-trifluoromethylbenzoic acid 3.00 g (13.5 mmol) of 3-fluoro-2-methyl-4-trifluoromethylbenzoic acid were initially charged in 50 ml of N, N-dimethylformamide. 1.68 g (60 wt.% Purity, 41.9 mmol) of NaH were added portionwise. To complete the gas separation 1.77 g (95 wt .-% purity, 27.0 mmol) of ethanethiol were added dropwise. The mixture was stirred for 2 h at rt and then heated to 80 ^° C. for 10 h. The reaction mixture was cooled, poured onto ice-water for work-up and then acidified with concentrated hydrochloric acid. The product precipitated and was separated via filtration. 3.7 g of the clean product were isolated. Step 3: Synthesis of 1-ethyl-4- (3 ^{'ethylthio-2'} -methyl-4 ^{'-trifluoromethyl)} benzoyl-5-hydroxypyrazole

300 mg (1.14 mmol) of 3-ethylthio-2-methyl-4-trifluoromethylbenzoic acid were initially charged in 20 ml of dry CH ₂ Cl _{2 and} admixed with 288 mg (2.27 mmol) of oxalic acid dichloride. The mixture was stirred for 15 min. heated to reflux, then no gas separation was observed. The contents were cooled to RT and concentrated. The acid chloride thus obtained was dissolved in 20 ml of dry CH ₂ Cb and the solution was added to a mixture of 140 mg (1.25 mmol) of 1-ethyl-5-hydroxypyrazole and catalytic amounts of 4-N, N-dimethylaminopyridine. Thereafter, 230 mg (2.27 mmol) of triethylamine were slowly added dropwise, and the reaction mixture was stirred at RT for 16 h. For workup, 3 ml of 1 M HCl were added and after the phase separation, the organic phase was freed from the solvent. The enol ester thus obtained was taken up in 20 ml of acetonitrile and 230 mg (2.27 mmol) of triethylamine were added.

Subsequently, eight drops of acetone cyanohydrin and a spatula tip KCN were added. The mixture was stirred at RT for 16 h and was then concentrated. The residue was mixed with 20 ml of CH ₂ Cl ₂ and then with 3 ml of 1 M HCl. After phase separation, the solvent was separated. The residue was purified by chromatography to isolate 182 mg of clean product.

Step 4: Synthesis of 1-ethyl-4- (3 ^{'-ethylsulfonyl-2'} -methyl-4 ^{'-trifluoromethyl)} benzoyl-5-hydroxypyrazole

182 mg (0:51 mmol) of 1-ethyl-4- (3 ^{'ethylthio-2'} -methyl-4 ^{'-trifluoromethyl)} benzoyl-5-hydroxypyrazole was dissolved in 20 ml CH ₂ CI ₂ and then with 376 mg (70 wt .-% purity, 1.52 mmol) Metachlorperbenzoesäure. Thereafter, the mixture was stirred at RT for 16 h. For workup, it was diluted with CH ₂ Cl ₂ and washed with 10% aqueous sodium hydrogen sulfite solution. It was acidified with 1 M HCl, then after the phase separation and after the analytical detection of the absence of peroxides, the organic phase was dried and freed from the solvent. The residue was purified by chromatography to isolate 88.8 mg of clean product. Preparation of 5-hydroxy-i, 3-dimethyl-4- (2 ^{'-methyl-3'-methylsulfonyl-4'} - trifluoromethyl) benzoylpyrazole Step 1: Synthesis of 2-methyl-3-methylthio-4-trifluoromethylbenzoic acid

300 mg (1.35 mmol) of 3-fluoro-2-methyl-4-trifluoromethylbenzoic acid were initially charged in 5 ml of N, N-dimethylformamide, and 59 mg (60% by weight of pure, 1.49 mmol) of NaH were added. The mixture was stirred for 10 min. stirred, then 199 mg (95 wt .-% purity, 2.70 mmol) of sodium thiomethylate were added. The mixture was stirred at RT for 1.5 h and then heated at 80 ^° C. for 16 h. The reaction mixture was cooled, poured onto water for work-up, extracted with ethyl acetate, and then the aqueous phase was acidified with concentrated HCl. The mixture was extracted twice with t-butyl methyl ether, dried and concentrated. 310 mg of the product were isolated.

Step 2: Synthesis of 2-methyl-3-methylsulfonyl-4-trifluoromethylbenzoic acid 1.50 g (5.99 mmol) of 2-methyl-3-methylthio-4-trifluoromethylbenzoic acid were initially charged in 20 ml of glacial acetic acid. 59 mg (0:18 mmol) of sodium tungstate (VI) dihydrate were added, after which the mixture was to 50 - 60 ⁰ C heated. At this temperature cautiously 2.45 ml (30%, 23.98 mmol) of an aqueous

Hydrogen peroxide solution added dropwise. The mixture was stirred for a few hours at this temperature until HPLC analysis indicated no more educt and no sulfoxide. The reaction mixture was cooled and poured onto water for work-up. The mixture was extracted three times with ethyl acetate, the combined organic phases were washed with an aqueous saturated sodium bisulfite solution, and after analytically detecting the absence of peroxides, the mixture was acidified with 1 M HCl. The organic phase was dried and freed from the solvents. 1.67 g of the clean product were isolated. Step 3: Synthesis of 5-hydroxy-1, 3-dimethyl-4- (2 ^'-methyl-3' -methylsulfonyl-4 ^'- trifluoromethyl) benzoylpyrazole

200 mg (0.71 mmol) of 2-methyl-3-methylsulfonyl-4-trifluoromethylbenzoic acid were together with 87 mg (0.78 mmol) of 5-hydroxy-1, 3-dimethylpyrazole and a catalytic amount of 4-N, N-dimethylaminopyridine in 20 ml of dry CH ₂ Cl ₂ and treated with 163 mg (0.85 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimid hydrochloride. The mixture was stirred at RT for 3 h and then treated with 3 ml of 1 M HCl. After phase separation, the aqueous phase was extracted with CH ₂ Cl ₂ . The organic phases were dried and concentrated. The residue was taken up in 20 ml of acetonitrile and 143 mg (1.42 mmol) of triethylamine and mixed with eight drops of acetone cyanohydrin and a spatula tip KCN. The mixture was stirred at RT for 16 h and was concentrated. The residue was treated with 15 ml of CH ₂ Cb and then with 2 ml of 1 M HCl. After phase separation, the aqueous phase was extracted with CH ₂ Cb. The combined organic phases were dried and concentrated. The residue was purified by chromatography. 112.7 mg of clean product were isolated.

The examples listed in the following tables were prepared analogously to the above-mentioned methods or are obtainable analogously to the methods mentioned above. These compounds are particularly preferred.

The abbreviations used mean:

Bu = butyl Et = ethyl Me = methyl Pr = propyl i = iso s = secondary t = tertiary Ph = phenyl

Table A: Compounds of the general formula (I) according to the invention, in which R ^{1 is} methyl, and R ² and Y are each hydrogen

Table B: Compounds of the general formula (I) according to the invention, in which R ^{1 is} ethyl, and R ² and Y are each hydrogen

Table C: Compounds of the general formula (I) according to the invention, in which R ¹ and R ^{2 are} each methyl, and Y is hydrogen

Table D: Compounds of the general formula (I) according to the invention

Table E: Compounds of the general formula (IIIb) according to the invention

Table F: Compounds of the general formula (IM) according to the invention

B. Formulation Examples

1. Dusts

A dust is obtained by mixing 10 parts by weight of a compound of general formula (I) and 90 parts by weight of talc as an inert material and comminuting in a hammer mill.

2. Dispersible powder

A wettable powder readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the general formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as a wetting and dispersing agent, and grinded in a pin mill.

3. Dispersion Concentrate A dispersion concentrate readily dispersible in water is obtained by adding 20 parts by weight of a compound of general formula (I), 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 Parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to about 277 ° C) mixed and ground in a ball mill to a fineness of less than 5 microns.

4. Emulsifiable concentrate

An emulsifiable concentrate is obtained from 15 parts by weight of a compound of general formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.

5. Water-dispersible granules

A water-dispersible granule is obtained by reacting 75 parts by weight of a compound of general formula (I), 10 "lignosulfonic acid calcium,

5 "sodium lauryl sulfate,

3 "polyvinyl alcohol and 7 "kaolin mixed, ground on a pin mill and the powder in a fluidized bed through

Spraying of water as granulating liquid granulated.

Water-dispersible granules are also obtained by mixing 25 parts by weight of a compound of general formula (I), 5 "2.2 ¹ -dinaphthylmethan-6,6'-disulfonate to,

2 "oleoylmethyl tauric acid sodium,

1 "polyvinyl alcohol, 17" calcium carbonate and

50 "of water homogenized on a colloid mill and pre-crushed, then grinded on a bead mill and the suspension thus obtained in a spray tower by means of a Einstoffdüse atomized and dried.

C. Biological examples

1. Herbicidal action against harmful plants in the pre-emergence

Seeds or rhizome pieces of monocotyledonous and dicotyledonous harmful plants are placed in sandy loam soil in pots of 9 to 13 cm in diameter and covered with soil. The formulated as emulsifiable concentrates or dusts herbicides are applied in the form of aqueous dispersions or suspensions or emulsions with a water cost amount of the equivalent of 300 to 800l / ha in different dosages on the surface of the cover soil. Subsequently, the pots are kept for optimal cultivation of the plants in the greenhouse under optimal conditions. The visual evaluation of the damage to the harmful plants takes place 3-4 weeks after the treatment. As the results of these comparative tables show, the selected compounds according to the invention have a better herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants than those disclosed in the prior art 2. Herbicidal action against harmful plants in postemergence Seeds of monocotyledonous and dicotyledonous harmful plants are laid out in sandy loam soil in cardboard pots, covered with soil and grown in the greenhouse under good growth conditions. Two to three weeks after sowing, the test plants are treated in a trefoil study. The compounds of the invention formulated as wettable powders or as emulsion concentrates are sprayed onto the surface of the green parts of plants at a rate of 600 to 800 l / ha of water in a dosage indicated in Tables 1 to 5. After 3 to 4 weeks of life of the test plants in the greenhouse under optimal growth conditions, the effect of the compounds according to the invention in comparison with compounds disclosed in the prior art, scored. As the results of these comparative tables show, the selected compounds according to the invention have a better herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants than those disclosed in the prior art.

The abbreviations used in the following comparison tables mean:

ABUTH Abutilon theophrasti AMARE Amaranthus retroflexus

AVEFA Avena fatua DIGSA Digitaria sanguinalis ECHCG Echinochloa crus galli GALAP Galium aparine

LOLMU Lolium multiflorum MATIN Matricaria inodora

POLCO Polygonum convolvulus SETVI Setaria viridis

STEME Stellaria media VERPE Veronica persica

VIOTR Viola tricolor XANST Xanthium strumarium STDT prior art Comparison Chart 1: pre-emergence

Comparison Chart 2: Pre-emergence

Comparison Chart 3: Postemergence

Comparison table 4: postemergence

Comparison Chart 5: Postemergence

Comparison Table 6: Pre-emergence

Comparison Table 7: Postemergence

Comparison Table 8: Pre-emergence

Comparison Chart 9: Preemergence

Comparison Chart 10: Postemergence

Comparison Chart 11: Post-emergence

Claims

claims:

1. 4- (4-trifluoromethyl-3-thiobenzoyl) pyτazoles of the formula (I) or salts thereof

wherein

R ¹ is (C ₁ -C ₄ ) -alkyl,

R ² is hydrogen or (C ₁ -C ₄ ) -alkyl,

R ³ is (C _r C ₄ ) -alkyl,

R ⁴ is (C ₁ -C ₄ ) -alkyl,

Y is hydrogen, (Ci-C ₆₎ alkylsulfonyl, (C _{r C4)} alkoxy- (Ci-C ₆₎ - alkylsulfonyl, or respectively by m identical or different radicals from the group consisting of halogen, (Ci-C ₄ ) -alkyl and (C 1 -C ₄ ) -alkoxy-substituted phenylsulfonyl, thiophenyl-2-sulfonyl, benzoyl, benzoyl- (C 1 -C 6) -alkyl or benzyl,

m is 0, 1, 2 or 3,

n is 0, 1 or 2.

2. 4- (4-trifluoromethyl-3-thiobenzoyl) pyrazoles of the formula (I) according to claim 1, wherein

R ¹ is methyl or ethyl, R ² is hydrogen, methyl or ethyl,

R ³ is methyl or ethyl,

R ⁴ is methyl or ethyl,

Y is hydrogen, (C 1 -C ₃ ) -alkylsulfonyl, (C 1 -C ₂ ) -alkoxy- (C 1 -C ₄ ) -alkylsulfonyl, or phenylsulfonyl which is each substituted by m-methyl groups, thiophenyl-2-sulfonyl, benzoyl, benzoyl- (C 1 -C ₆ ) - alkyl or benzyl,

m is 0 or 1,

n is 0, 1 or 2.

3. 4- (4-trifluoromethyl-3-thiobenzoyl) pyrazoles of the formula (I) according to claim 1, in which R ¹ denotes methyl or ethyl,

R ² is hydrogen, methyl or ethyl,

R ³ is methyl or ethyl,

R ⁴ is methyl or ethyl,

Y is hydrogen,

n is 0, 1 or 2.

4. A herbicidal composition, characterized by a herbicidally active content of at least one compound of the formula (I) according to one of claims 1 to 3.

5. A herbicidal composition according to claim 4 in admixture with formulation auxiliaries.

6. A method for controlling unwanted plants, characterized in that an effective amount of at least one compound of formula (I) according to any one of claims 1 to 3 or a herbicidal composition according to claim 4 or 5 on the plants or on the location of undesired plant growth applied.

7. Use of compounds of the formula (I) according to any one of claims 1 to 3 or of herbicidal compositions according to claim 4 or 5 for controlling unwanted plants.

8. Use according to claim 7, characterized in that the compounds of formula (I) are used for controlling undesirable plants in crops of crops.

9. Use according to claim 8, characterized in that the crops are transgenic crops.

10. Compounds of the formula (III)

wherein R ³ , R ⁴ and n are as defined in any one of claims 1 to 3.

11. Compounds of the formula (UIb)

wherein R, R and n are as defined in any one of claims 1 to 3.